Structural and Magnetic Phase Transformations of Hydroxyapatite-Magnetite Composites under Inert and Ambient Sintering Atmospheres

The present work reports the impact of sintering conditions on the phase stability in hydroxyapatite (HA) magnetite (Fe3O4) bulk composites, which were densified using either pressureless sintering in air or by rapid densification via hot pressing in inert atmosphere. In particular, the phase abundances, structural and magnetic properties of the (1-x)HA-xFe(3)O(4) (x = 5, 10, 20, and 40 wt %) composites were quantified by corroborating results obtained from Rietveld refinement of the X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy. Post heat treatment phase analysis revealed a major retention of Fe3O4 in argon atmosphere, while it was partially/completely oxidized to hematite (alpha-Fe2O3) in air. Mossbauer results suggest the high-temperature diffusion of Fe3+ into hydroxyapatite lattice, leading to the formation of Fe-doped HA. A preferential occupancy of Fe3+ at the Ca(1) and Ca(2) sites under hot-pressing and conventional sintering conditions, respectively, was observed. The lattice expansion in HA from Rietveld analysis correlated well with the amounts of Fe-doped HA determined from the Mossbauer spectra. Furthermore, hydroxyapatite in the monoliths and composites was delineated to exist in the monoclinic (P2(1)/b) structure as against the widely reported hexagonal (P6(3)/m) crystal lattice. The compositional similarity of iron doping in hydroxyapatite to that of tooth enamel and bone presents HA-Fe3O4 composites as potential orthopedic and dental implant materials.

Size Dependent Magnetic Properties of Nd0.7Ca0.3MnO3 Nanomanganite

Nanoscale materials show different properties compared to bulk materials. Due to the size dependent properties the nanoscale materials have potential applications in industry. In this paper the size dependent magnetic properties of Nd0.7Ca0.3MnO3 nanomanganite have been investigated. Nd0.7Ca0.3MnO3 nanoparticles were prepared by low temperature sol-gel method. X-ray diffraction (XRD), Transmission Electron Microscopy (TEM) and EDAX techniques were used to understand the structure, grain size and composition. Nanoparticles prepared were of the sizes 15 nm, 19 nm and 25 nm respectively. SQUID magnetometer was used to study the magnetic behavior of the nanoparticles. Field cooled (FC) and zero field cooled (ZFC) magnetization of all the nanosamples with respect to temperature was studied and compared. We have observed drastic changes in magnetic properties of 15 nm particles compared to the other nanoparticles. The `charge order peak' was seen to have disappeared in 15 nm particles while it was present in the other nanoparticles. All the nano particles exhibit superparamagnetism whose blocking temperature decreases as a function of decreasing particle size. The possible reasons for the influence of the particle size on the magnetic properties are discussed.

Synthesis, characterization and low temperature electrical conductivity of Polyaniline/NiFe2O4 nanocomposites

Conducting polymer/ferrite nanocomposites with an organized structure provide a new functional hybrid between organic and inorganic materials. The most popular among the conductive polymers is the polyaniline (PANI) due to its wide application in different fields. In the present work nickel ferrite (NiFe2O4) nanoparticles were prepared by sol-gel citrate-nitrate method with an average size of 21.6nm. PANI/NiFe2O4 nanoparticles were synthesized by a simple general and inexpensive in-situ polymerization in the presence of NiFe2O4 nanoparticles. The effects of NiFe2O4 nanoparticles on the dc-electrical properties of polyaniline were investigated. The structural components in the nanocomposites were identified from Fourier Transform Infrared (FTIR) spectroscopy. The crystalline phase of nanocomposites was characterized by X-Ray Diffraction (XRD). The Scanning Electron Micrograph (SEM) reveals that there was some interaction between the NiFe2O4 particles and polyaniline and the nanocomposites are composed of polycrystalline ferrite nanoparticles and PANI. The dc conductivity of polyaniline/NiFe2O4 nanocomposites have been measured as a function of temperature in the range of 80K to 300K. It is observed that the room temperature conductivity sigma(RT) decreases with increase in the relative content of NiFe2O4. The experimental data reveals that the resistivity increases for all composites with decrease of temperature exhibiting semiconductor behaviour.

Doping effect of Ag+, Mn2+ ions on Structural and Optical Properties of ZnO nanoparticles

Pure ZnO and co-doped (Mn, Ag) ZnO nanoparticles have been successfully prepared by chemical co-precipitation method without using a capping agent. X-ray diffraction (XRD) studies confirms the presence of wurtzite (hexagonal) crystal structure similar to undoped ZnO, suggesting that doped Mn, Ag ions are substituted to the regular Zn sites. The morphology of the samples were studied by scanning electron microscopy (SEM). The chemical composition of pure and co-doped ZnO nanoparticles were characterized by energy dispersive X-ray analysis spectroscopy (EDAX). Optical absorption properties were determined by UV-vis Diffuse Reflectance Spectrophotometer. The incorporation of Ag+, Mn2+ in the place of Zn2+ provoked to decrease the size of nanocrystals as compared to pure ZnO. Optical absorption measurements indicates blue shift in the absorption band edge upon Ag, Mn ions doped ZnO nanoparticles.

Thermoelectric properties of Pb0.75-xMnxSn0.25Te alloys with variable manganese content

Lead tin telluride is one of the well-established thermoelectric materials in the temperature range 350-750 K. In the present study, Pb0.75-xMnxSn0.25Te1.00 alloys with variable manganese (Mn) content were prepared by solid state synthesis and the thermoelectric properties were studied. X-ray diffraction, (XRD) showed that the samples followed Vegard's law, indicating solid solution formation and substitution of Mn at the Pb site. Scanning Electron Microscopy (SEM) showed that the grain sizes varied from <1 mu m to more than 10 mu m and MnTe rich phase was present for higher Mn content. Seebeck coefficient, electrical resistivity and thermal conductivity were measured from room temperature to 720 K. At 300 K, large Seebeck values were obtained, possibly due to increased effective mass on Mn substitution and low carrier concentration of the samples. At higher temperatures, transition from n-type to p-type indicated the presence of thermally generated carriers. Temperature dependent electrical resistivity showed the transition from degenerate to non-degenerate behavior. For thermal conductivity, low values (similar to 1 W/m-K at 300 K) were obtained. At higher temperatures bipolar conduction was observed, in agreement with the Seebeck and resistivity data. Due to low power factor, the maximum thermoelectric figure of merit (zT) was limited to 0.23 at 329 K for the sample with lowest Mn content (x=0.03). (C) 2015 Elsevier Ltd. All rights reserved.

Piezoelectric properties of individual nanocrystallites of Ba0.85Ca0.15Zr0.1Ti0.9O3 obtained by oxalate precursor route

Nanocrystalline Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) powder was synthesized via the complex oxalate precursor route at a relatively low temperature (800 degrees C/5 h). The phase formation temperature of BCZT at nanoscale was confirmed by thermogravimetric (TG), differential thermal analysis (DTA) followed by X-ray powder diffraction (XRD) studies. Fourier transform infrared (FTIR) spectroscopy was carried out to confirm the complete decomposition of oxalate precursor into BCZT phase. The XRD and profile fitting revealed the coexistence of cubic and tetragonal phases and was corroborated by Raman study. Transmission electron microscopy (TEM) carried out on 800 degrees C and 1000 degrees C/5 h heat treated BCZT powder revealed the crystallite size to be in the range of 20-50 nm and 40-200 nm respectively. The optical band gap for BCZT nanocrystalline powder was obtained using Kubelka Munk function and was found to be around 3.12 +/- 0.02 eV and 3.03 +/- 0.02 eV respectively for 800 degrees C (20-50 nm) and 1000 degrees C/5 h (40-200 nm) heat treated samples. The piezoelectric properties were studied for two different crystallite sizes (30 and 70 nm) using a piezoresponse force microscope (PFM). The d(33) coefficients obtained for 30 nm and 70 nm sized crystallites were 4 pm V-1 and 47 pm V-1 respectively. These were superior to that of BaTiO3 nanocrystal (approximate to 50 nm) and promising from a technological/industrial applications viewpoint.

Ni Nano-particle Encapsulated in Hollow Carbon Sphere Electrocatalyst in Polymer Electrolyte Membrane Water Electrolyzer

The present study evaluates the synthesis by solvo-thermal method and electrocatalytic activity of nickel nano-particles encapsulated in hollow carbon sphere, in hydrogen and oxygen evolution reaction in PEM water electrolyzer. The XRD patterns have ascertained the formation of nickel metal with different planes in face centered cubic (fcc) and hexagonal closed pack (hcp) form. SEM and TEM images have confirmed the nickel nano-particles with diameter of 10-50 nm inside the 0.2 mu m sized hollow carbon spheres. The BET surface area values gradually decreased with greater encapsulation of nickel; although the electrochemical active surface area (ECSA) values have been calculated as quite higher. It confirms the well dispersion of nickel in the materials and induces their electrocatalytic performance through the active surface sites. The cyclic voltammetric studies have evaluated hydrogen desorption peaks as five times more intense in nickel encapsulated materials, in comparison to the pure hollow carbon spheres. The anodic peak current density value has reached the highest level of 1.9 A cm(-2) for HCSNi10, which gradually decreases with lesser amount of nickel in the electrocatalysts. These electrocatalysts have been proved electrochemically stable during their usage for 48 h long duration under potentiostatic condition. (C) 2015 Elsevier Ltd. All rights reserved.

Ag2S sensitized mesoporous Bi2WO6 architectures with enhanced visible light photocatalytic activity and recycling properties

To harvest solar energy more efficiently, novel Ag2S/Bi2WO6 heterojunctions were synthesized by a hydrothermal route. This novel photocatalyst was synthesized by impregnating Ag2S into a Bi2WO6 semiconductor by a hydrothermal route without any surfactants or templates. The as prepared structures were characterized by multiple techniques such as X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmet-Teller (BET) analysis, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDS), UV-vis diffuse reflection spectroscopy (DRS) and photoluminescence (PL). The characterization results suggest mesoporous hierarchical spherical structures with a high surface area and improved photo response in the visible spectrum. Compared to bare Bi2WO6, Ag2S/Bi2WO6 exhibited much higher photocatalytic activity towards the degradation of dye Rhodamine B (RhB). Although silver based catalysts are easily eroded by photogenerated holes, the Ag2S/Bi2WO6 photocatalyst was found to be highly stable in the cyclic experiments. Based on the results of BET, Pl and DRS analysis, two possible reasons have been proposed for the enhanced visible light activity and stability of this novel photocatalyst: (1) broadening of the photoabsorption range and (2) efficient separation of photoinduced charge carriers which does not allow the photoexcited electrons to accumulate on the conduction band of Ag2S and hence prevents the photocorrosion.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Effect of the nature of a transition metal dopant in BaTiO3 perovskite on the catalytic reduction of nitrobenzene

In the present study, we have synthesized Fe, Co and Ni doped BaTiO3 catalyst by a wet chemical synthesis method using oxalic acid as a chelating agent. The concentration of the metal dopant varies from 0 to 5 mol% in the catalysts. The physical and chemical properties of doped BaTiO3 catalysts were studied using various analytical methods such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), BET surface area and Transmission electron microscopy (TEM). The acidic strength of the catalysts was measured using a n-butylamine potentiometric titration method. The bulk BaTiO3 catalyst exhibits a tetragonal phase with the P4mm space group. A structural transition from tetrahedral to cubic phase was observed for Fe, Co and Ni doped BaTiO3 catalysts with an increase in doped metal concentration from 1 to 5 mol%. The particle sizes of the catalysts were calculated from TEM images and are in the range of 30-80 nm. All the catalysts were tested for the catalytic reduction of nitrobenzene to azoxybenzene. The BaTiO3 catalyst was found to be highly active and less selective compared to the doped catalysts which are active and highly selective towards azoxybenzene. The increase in selectivity towards azoxybenzene is due to an increase in acidic strength and reduction ability of the doped metal. It was also observed that the nature of the metal dopant and their content at the B-site has an impact on the catalytic reduction of nitrobenzene. The Co doped BaTiO3 catalyst showed better activity with only 0.5 mol% doping than Fe and Ni doped BaTiO3 catalysts with maximum nitrobenzene conversion of 91% with 78% selectivity to azoxybenzene. An optimum Fe loading of 2.5 mol% in BaTiO3 is required to achieve 100% conversion with 93% selectivity whereas Ni with 5 mol% showed a conversion of 93% and a azoxybenzene selectivity of 84%.

Pt-Doped and Pt-Supported La1-xSrxCoO3: Comparative Activity of Pt4+ and Pt-0 Toward the CO Poisoning Effect in Formic Acid and Methanol Electro-oxidation

Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3 are synthesized using chemical reduction and solution combustion method, respectively. Chemical reduction is carried out using formaldehyde as a reducing agent giving Pt-supported La1-xSrxCoO3. Solution combustion method is used to prepare Pt-doped La1-xSrxCoO3. Detailed characterization using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurement, and transmission electron microscopy (TEM) is carried out to distinguish the Pt-supported and Pt-doped compounds in terms of their morphology and Pt oxidations states. TEM results indeed show the differences in their morphology. Further, electrochemical measurements are performed in neutral medium to differentiate their electrochemical activity. Cyclic voltammetry (CV) shows noticeable differences between Pt-supported La1-xSrxCoO3 and Pt-doped La1-xSrxCoO3. Importantly, our results show that Pt4+ in doped compound has poor to zero electrocatalytic activity toward formic acid and methanol electro-oxidation in comparison to Pt-0 in supported compound. This study shows that metallic Pt in zero oxidation state is a superior catalyst to Pt in +4 oxidation state.

On the Room Temperature Ferromagnetic and Ferroelectric Properties of Pb(Fe1/2Nb1/2)O-3

We report the origin of room temperature (RT) ferromagnetic and ferroelectric properties of Pb(Fe1/2Nb1/2)O-3 (PFN) ceramic sample prepared by modified solid-state reaction synthesis by a single-step method, based on X-ray diffraction (XRD), neutron diffraction (ND), Mossbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy results. Formation of single-phase monoclinic PFN ceramic with Cm space group was confirmed by XRD and ND at RT. The morphology studied by scanning electron microscopy (SEM) confirmed uniform microstructure of the sample with average grain size of similar to 2 mu m. The ND, Mossbauer spectroscopy, M-H loop and EPR studies were carried out to confirm the existence of weak ferromagnetism at RT. A clear opening of hysteresis (M-H) loop is evidenced as the existence of weak ferromagnetism at RT. EPR spectrum clearly shows the ferromagnetism through a good resonance signal. The symmetric EPR line shape with g = 1.9895 observed in PFN sample was identified to be due to Fe3+ ions. Mossbauer spectroscopy at RT shows superparamagnetic behaviour with presence of Fe in 3+ valence state. Ferroelectric P-E loops on PFN at RT confirm the existing ferroelectric ordering. Our observation is in agreement with literature, and it supports that the origin of ferromagnetism and ferroelectricity is isolated, i.e. from different regions in the sample. Our results do not support the multiferroic nature of PFN at RT.

Improved capacity and stability of integrated Li and Mn rich layered-spinel Li1.17Ni0.25Mn1.08O3 cathodes for Li-ion batteries

A Li-rich layered-spinel material with a target composition Li1.17Ni0.25Mn1.08O3 (xLiLi1/3Mn2/3]O-2.(1 - x) LiNi0.5Mn1.5O4, (x = 0.5)) was synthesized by a self-combustion reaction (SCR), characterized by XRD, SEM, TEM, Raman spectroscopy and was studied as a cathode material for Li-ion batteries. The Rietveld refinement results indicated the presence of monoclinic (LiLi1/3Mn2/3]O-2) (52%), spinel (LiNi0.5Mn1.5O4) (39%) and rhombohedral LiNiO2 (9%). The electrochemical performance of this Li-rich integrated cathode material was tested at 30 degrees C and compared to that of high voltage LiNi0.5Mn1.5O4 spinel cathodes. Interestingly, the layered-spinel integrated cathode material exhibits a high specific capacity of about 200 mA h g(-1) at C/10 rate as compared to 180 mA h g(-1) for LiNi0.5Mn1.5O4 in the potential range of 2.4-4.9 V vs. Li anodes in half cells. The layered-spinel integrated cathodes exhibited 92% capacity retention as compared to 82% for LiNi0.5Mn1.5O4 spinel after 80 cycles at 30 degrees C. Also, the integrated cathode material can exhibit 105 mA h g(-1) at 2 C rate as compared to 78 mA h g(-1) for LiNi0.5Mn1.5O4. Thus, the presence of the monoclinic phase in the composite structure helps to stabilize the spinel structure when high specific capacity is required and the electrodes have to work within a wide potential window. Consequently, the Li1.17Ni0.25Mn1.08O3 composite material described herein can be considered as a promising cathode material for Li ion batteries.

Design and morphology control of a thiophene derivative through electrospraying using various solvents

In the present work, electrospraying of an organic molecule is carried out using various solvents, obtaining fibril structures along with a range of distinct morphologies. Solvent characteristics play a major role in determining the morphology of the organic material. A thiophene derivative (7,9-di(thiophen-2-yl)-8H-cyclopentaa]acenaphthylen-8-one) (DTCPA) of donor-acceptor-donor (DAD) architecture is used to study this solvent effect. Seven solvents with decreasing vapour pressure are selected for experiments. Electrospraying is conducted at a solution concentration of 1.5 wt% and a constant applied voltage of 15 kV. Gradual transformation in morphology of the electrospun product from spiked-spheres to only spikes is observed. A mechanism describing this transformation is proposed based on electron micrograph analysis and XRD analysis. These data indicate that the morphological change is due to the synergistic effect of both vapour pressure and dielectric constant of the solvents. Through a reasonable control of the crystallite size and morphology along with the proposal of the transformation mechanism, this study elucidates electrospraying as a prospective method for designing architectures in organic electronics.

Robust, metallic Pd17Se15 and Pd7Se4 phases from a single source precursor and their use as counter electrodes in dye sensitized solar cells

Thin films of conducting palladium selenide phases (Pd17Se15 and Pd7Se4) are prepared using a single source molecular precursor by thermolysis. Varying the mole ratios of palladium and selenium precursors results in palladium organo-selenolate complexes which on thermolysis at different temperatures yield Pd17Se15 and Pd7Se4 phases that are very stable and adherent to the substrate. The organo-selenolate complexes are characterized using small angle XRD, Se-77 NMR and thermogravimetric analysis (TGA). The palladium selenide films are characterized by various techniques such as XRD, XPS, TEM and SEM. Electrical conductivities of the films are determined using the four probe method. The strong adherence of the films to glass substrates coupled with high corrosion resistant behavior towards strong acid and alkaline environments render them to be very effective as electrocatalysts. The catalytic activity towards the I-3(-)/I- redox couple, which is an important reaction in the regeneration of the dye in a dye-sensitized solar cell, is studied. Between the two phases, the Pd17Se15 film shows superior activity as the counter electrode for dye sensitized solar cells with a photocurrent conversion efficiency of 7.45%.